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Macromolecular chain scission under mechanical stress has been studied by infrared spectroscopy. The dependence of accumulation of chemical bond scissions on temperature T and uniaxial tensile stress σ has been investigated. The rate constant K for bond dissociation under mechanical stress has been found to obey the modified Arrhenius equation: K = K0 exp{ − (EA − ασ)/RA}. The quantitative connection between the rate constant for bond dissociation and mechanical lifetime τ has been established. Analysis of the experimental data indicates that the strength and mechanical lifetime of polymers is determined by the kinetics of mechanochemical scission of the main chains of polymer molecules.

SynopsisSubmicrocracks, free radicals, and endgroups of scissioned molecules formed in polyethylene, polypropylene, and polycaprolactam under uniaxial tension have been investigated. Measurements were carried out by small-angle x-ray scattering, electron paramagnetic resonance, and infrared spectroscopy. The concentration of submicrocracks is almost the same as that of free radicals but is smaller than the concentration of scissioned macromolecules by approximately three orders of magnitude. The number of scissions per crack proved to be close to the number of macromolecules passing through the cross section of a submicrocrack calculated on the assumption of close packing. It is concluded that submicrocracks in stressed polymers are formed as a result of chain reactions of macromolecular decomposition initiated by the active end primary free radicals. 1509

A B S T R A C T Formation of incipient submicroscopic cracks in polymers under load have been studied by small-angle X-ray scattering. The main regularities of crack formation under different loading conditions have been analyzed. The connection between the submicrocrack concentration and the deformation of a stressed polymer has been shown. The main parameters of crack formation defining the strength properties of a polymer, i.e., the size of initial submicrocracks transverse to the axis of loading, which is determined by the structural heterogeneity of a material, and the concentration of submicrocracks before rupture, have been established. The analysis of the quantitative correlation between these parameters allows one to formulate the main statements regarding the micromechanics of polymer fracture. From comparing the volume and surface parameters of crack formation of a stressed polymer, the dominating role of the surface in the process of fracture has been demonstrated.